Self-supporting NOx reducing catalyst

ABSTRACT

A system for reducing NO x  gases found in the exhaust stream of the internal combustion engine is provided which includes an internal combustion engine having associated therewith a means for supplying fuel and oxygen to the engine, a manifold system for directing or channeling the exhaust gases from the engine, and a NO x  reducing catalyst assembly communicating with the manifold which includes a housing having a NO x  reducing catalytic structure of apertured thin metal foil positioned therein which comprises a durable, chromium containing corrosion resistant nickel base substrate having metallurgically bonded thereto, on at least one surface, an effective amount of a NO x  reducing catalyst selected from the group consisting of iron, nickel, cobalt, copper, manganese and mixtures thereof.

BACKGROUND OF THE INVENTION

This is a continuation of application Ser. No. 453,567 filed Mar. 22, 1974, now abandoned, which is a continuation-in-part of U.S. patent application Ser. No. 207,337, filed 12/31/71, which, in turn, is a continuation-in-part of U.S. patent application Ser. No. 149,331, filed 6/2/71, now all abandoned.

This invention relates to a system of operating an internal combustion engine and includes the use of a catalytic structure capable of reducing oxides of nitrogen, especially nitric oxide and nitrogen dioxide (herein collectively referred to as NO_(x)), which are found in the exhaust gases emanating from the internal combustion engine. In addition, it concerns a catalytic structure comprising a durable, corrosion resistant nickel base substrate having an effective amount of a NO_(x) reducing catalyst metallurgically bonded thereto. Such a catalytic structure is characterized by its corrosion resistance and is especially effective in reducing the oxides of nitrogen at temperatures of about 1100° F and above.

DESCRIPTION OF THE PRIOR ART

Many undesirable gases are found in the exhaust stream emanating from the internal combustion engine. Some of the most harmful and annoying of these gases are carbon monoxide, unburned hydrocarbons and the oxides of nitrogen.

Presently, much effort is being directed to the removal of carbon monoxide and unburned hydrocarbons by thermal or catalytic oxidation, and to the diminution or elimination of the oxides of nitrogen by catalytic reduction.

With regard to the various oxides of nitrogen, herein referred to as NO_(x), it is the present desire to eliminate at least 90% of the NO_(x) issuing from the typical internal combustion engine, using the 1971 U.S.A. model automotive vehicle as the base.

In the prior art, references can be found which concern certain catalysts that are, at least theoretically, capable of reducing NO_(x) to less harmful substances. However, such prior art is devoid of any reference or teaching which concerns a durable, economical catalyst system which is especially well suited for use in the operating environment associated with today's automobiles.

In the main, this is due to the fact that the present stringent NO_(x) reduction requirements necessitate the operation of the catalyst in a corrosive atmosphere at unusualy high temperatures. For example, under normal operating conditions in a conventional internal combustion engine, such a catalyst is often exposed to temperatures ranging from about 1100° F to 1700° F, and higher. Under these operating conditions, it has heretofore been essentially impossible to find a NO_(x) reducing catalyst which evidences the requisite catalytic efficiency and also possesses the necessary structural durability.

As typical of the prior art, tests have been published indicating that nickel-copper alloys are very active catalytic NO_(x) reduction devices. In use, these catalytic devices are formed into Berl saddles to increase the surface area and to provide for a relatively low pressure catalyst containing assembly. However, in actual operation, experience has indicated that nickel-copper alloys have an oxidation limit of about 1300° F, or slightly higher, whereas present day internal combustion engines have an efflux temperature, during some part of the normal operating cycle, of up to about 1900° F. Such high temperatures cause a rapid deterioration of the catalyst and substantially reduce its effective life span. Furthermore, the preferred structure of prior art devices, such as the saddles mentioned above, are caused at high temperatures to be sintered together to a point where eventually significant gas blockage occurs. Thus, while copper-nickel alloys are sufficiently active in reducing up to 90% of the NO_(x) present, they are impractical at this time due to a lack of durability.

An extensive analysis of various catalytic structures and the problems pertaining thereto was published by the Society of Automotive Engineers on July 11, 1971, in SAE Paper No. 710291, entitled "NO_(x) Reduction Catalysts for Vehicle Emission Control". This article includes the disclosure of a composite of copper and stainless steel in the form of wire mesh screen. Still other approaches are indicated in U.S. Pat. No. 3,565,574 and British Pat. No. 1,058,706. The latter discloses a ceramic substrate and is thus representative of a catalyst in which the activating, or NO_(x) reducing material, does not withstand high temperatures by itself but must be supported by a suitable substrate.

In general, it may be summarized that presently known catalyst structures have failed to provide the required degree of NO_(x) reduction due to a lack of structural rigidity at high temperatures, insufficient corrosion resistance, back-pressure build up due to agglomeration, spalling of the catalytically active surface, or a combination of any or all of these shortcomings.

The instant invention overcomes the hereinbefore set forth types of problems associated with prior art devices by providing a system for operating an internal combustion engine which includes the use of a durable, efficient NO_(x) reducing catalytic structure comprising a corrosion resistant substrate having an effective amount of a suitable NO_(x) reduction catalyst metallurgically bonded thereto.

SUMMARY OF THE INVENTION

According to one aspect of the invention, a system for reducing NO_(x) gases found in the exhaust stream of the internal combustion engine is provided which includes an internal combustion engine having associated therewith a means for supplying fuel and oxygen to the engine, a manifold system for directing or channeling the exhaust gases from the engine, and a NO_(x) reducing catalyst assembly communicating with the manifold which includes a housing having a NO_(x) reducing catalytic structure of apertured thin metal foil positioned therein which comprises a durable, chromium containing corrosion resistant nickel base substrate having on at least one surface, an effective amount of a NO_(x) reducing catalyst selected from the group consisting of iron, nickel, cobalt, copper, manganese and mixtures thereof.

According to another aspect, the present invention is accomplished by providing a NO_(x) reducing catalytic structure comprising a durable, corrosion resistant nickel base support or substrate having an effective amount of a NO_(x) reducing catalyst metallurgically bonded thereto.

As used herein the term "nickel base substrate" shall mean a substrate wherein the weight percent of nickel always exceeds the individual weight percent of any other filler material, viz., cobalt and/or iron.

In addition, as used herein the term "metallurgically bonded" shall mean bonded together by the formation of a localized alloy.

More specifically, the catalytic structure of the instant invention comprises a chromium containing nickel base substrate, which may also optionally contain trace amounts of iron and/or cobalt, having a NO_(x) reducing catalyst metallurgically bonded to at least one surface of the substrate. However, it should be noted here that the nickel base substrate used in the instant invention may be devoid of any cobalt and/or iron, if desired. The term "trace amounts" as used herein shall mean individual amounts of iron or cobalt ranging from a detectable amount up to 1 weight percent. In this system, chromium is an oxide former and imparts corrosion resistance to the substrate, whereas nickel, cobalt and iron are filler materials which impart strength and mass to the substrate. The amount of filler material in the substrate can range from about 50 to about 85 weight percent, with the remainder usually being chromium. In the nickel base system of the present invention, if desired, up to 1 weight percent of both cobalt and iron can be added to substrate composition. In such a nickel base system, the minimum nickel content is about 48 weight percent of the substrate. In addition, aluminum can be included in the substrate composition of the invention. However, when aluminum is substituted for some of the chromium, the total weight percent of aluminum plus chromium cannot exceed about 50 weight percent.

Perhaps, it should be noted here that under certain conditions, it may be desirable to form the substrate from different alloy systems. See commonly assigned copending U.S. patent applications, Ser. Nos. 207,525; 207,284; 207,303; and 207,281, entitled Cobalt Base NO_(x) Reducing Catalytic Structure, Nickel Base NO_(x) Reducing Catalytic Structure, Chromium Containing Iron Base NO_(x) Reducing Catalytic Structure and Aluminum Containing Iron Base NO_(x) Reducing Catalytic Structure, respectively, filed Dec. 13, 1971.

The type and amount of NO_(x) reducing catalyst which may be metallurgically bonded to the hereinbefore described substrate depends to a large degree on the environment in which the catalytic structure will be utilized. In exhaust gases emanating from the internal combustion engine, NO_(x) catalysts selected from the group consisting of nickel, iron, cobalt, manganese, copper and mixtures threof have been found to be especially effective. The main criteria for a suitable NO_(x) catalyst is that (1) it does not deleteriously react with the substrate and (2) it is effective in reducing NO_(x) gases at the temperature of intended use.

With regard to the effectiveness of the NO_(x) catalyst, it should be pointed out that when using the hereinbefore described substrate care should be taken to avoid or minimize the migration of chromium and/or aluminum to the surface of the NO_(x) catalyst, as such substances reduce catalyst efficiency. From a practical standpoint, when operating at temperatures ranging from about 1100° F to about 1700° F, i.e., at temperatures usually experienced in today's automobiles, the individual chromium and aluminum content on the surface of the NO_(x) catalyst should be less than about 15 and 4 weight percent, respectively. However, it should be pointed out here that when operating at higher temperatures and/or under different air to fuel ratios, it may be possible to tolerate a slightly higher weight percentage of chromium and/or aluminum on the surface of the catalytic layer and still have an efficient catalytic system. As used herein the term "surface of the catalytic layer" shall mean the volume defined by the area covered by the catalytic material taken to the depth measurable by a 20,000 volt microprobe, i.e., approximately 50 to 80 microinches in depth.

After the catalytic layer has been metallurgically bonded to the substrate, the catalytic layer can be differentitated from the substrate by the amount and distribution of chromium and/or aluminum (oxide formers) found in these respective sections of the resultant catalytic structure. In a system wherein the only oxide former used is chromium, as before noted, the amount of chromium present in the substrate can range from about 15 to about 50 weight percent. In the resultant catalytic structure, in weight percent, there usually is less chromium (oxide former) in the catalytic layer than in the substrate proper. In actual practice there usually is a gradient of chromium throughout the catalytic structure ranging from a point of maximum concentration in the substrate (at least 15 weight percent chromium) to a point of relatively low concentration in the catalytic layer (not greater than 15 weight percent at the surface of the catalyst zone). That is, the catalytic layer usually contains a lower weight percent of chromium than does the substrate. Stating it functionally, the substrate contains enough chromium to render it resistant to corrosion, whereas the catalyst layer contains none or minimum amounts of chromium so as to not impair its ability to function as a NO_(x) reducing catalyst.

By utilizing the teaching of the instant invention, it is possible to obtain a NO_(x) reducing catalytic structure which is highly efficient and exceptionally durable, i.e. resistant to attrition and corrosion.

Accordingly, a major object of the invention is to provide a system for catalytically reducing NO_(x) found in the exhaust gases of the internal combustion engine.

A further object of the invention is to provide a catalytic structure which combines high NO_(x) reducing activity with high structural stability and which is especially effective at the level of elevated temperatures normally experienced in the exhaust gases of the internal combustion engine.

Other objects and the means of accomplishing them will be apparent to those skilled in the art from the following description and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plan view of the catalytic structure of the invention in the form of a sheet of expanded metal foil;

FIG. 2 is an enlarged plan view of the rectangular area of the catalytic structure shown in FIG. 1;

FIG. 3 is a cross-sectional view taken along line 3--3 of FIG. 2 of the catalytic structure of the invention; and

FIG. 4 is a diagrammatical illustration of the system of the invention.

In the above-identified drawings like parts are indicated by the like numerals. Specifically,in FIG. 1 is shown an expanded metal foil catalytic structure 10 comprised of a plurality of strands 12 which define apertures 14; in FIG. 2 the strands 12 and apertures 14 defined thereby are shown in an enlarged manner; in FIG. 3 a cross-sectional view on the strands 12 is shown.

In FIG. 4 there is shown the system of the invention for catalytically reducing NO_(x) found in the exhaust stream of the internal combustion engine which system includes an internal combustion engine 20 having communicating therewith a source of fuel 22 and a source 24 of an oxidant (oxygen from air) for the fuel. During operation of the internal combustion engine 20 exhaust gases are generated which pass through the manifold or conduit 26 into the NO_(x) reducing catalyst assembly or apparatus 28 which includes a housing 30 having a NO_(x) reducing catalyst structure 32 composed of a sheet of expanded thin metal foil of the type and composition described herein with a suitable nickelcopper NO_(x) reducing catalyst material deposited on the surface thereof positioned therein. The exhaust gases, after NO_(x) reduction, then exit from port 34. The so-treated gases are characterized by the fact that a significant amount of NO_(x) has been removed therefrom.

In the dual bed system, after the NO_(x) reduction treatment, the exhaust gases are then brought into contact with an oxidation catalyst to remove carbon monoxide and gaseous hydrocarbons therefrom. As such oxidation catalysts are well known in the art, they will not be discussed herein in detail.

DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

In the preferred embodiment of the invention, the herein described catalytic structure is formed from an expanded metal foil which, in turn, is stamped or otherwise fashioned into a suitable configuration, such as a disc, helical coil, corrugated strip, or the like, to provide a high surface, low mass catalyst assembly.

The catalytic structure of the inventin is physically composed of a plurality of different zones or regions comprising a corrosion resistant substrate and a NO_(x) reducing catalyst layer metallurgically bonded to the substrate in such a manner that the chemical composition of the substrate is different than the chemical composition of the catalytic layer. The invention is best explained by the following preferred process sequence for making a chromium containing nickel base substrate having a copper and/or nickel NO_(x) catalyst metallurgically bonded thereto.

The starting material is a conventional electroplated nickel foil produced continuously on a drum using a sulfamate bath. This produces commercially pure nickel which can contain up to about 1% by weight cobalt. All other impurities are present in fairly negligible amounts.

The nickel foil is, optionally, annealed in a furnace at a suitable temperature and thereafter expanded to provide an apertured metal structure having a thickness of less than about 10 mils. The annealing step facilitates the expanding operation only and appears to be otherwise not necessary. As the expanding process is well known, it will not be described herein in detail.

Subsequently, the expanded nickel foil is placed into a suitable, electrically conductive bath to uniformly electrodeposit thereon commercially pure chromium. The amount of chromium deposited is so controlled that chromium wil constitute about 15 to about 50 weight percent of the resultant substrate. It has been found that a substrate having a chromium content of less than about 15 to 18 weight percent, depending on the operational characteristics of the engine in which it is to be used, do not provide enough high temperature corrosion resistance. Also, data has indicated that exceeding the upper range of chromium content imparts poor formability to the resultant structure.

The chromium coating on the apertured substrate, which is still predominantly in elemental form at this point, is alloyed with the substrate material by a thermal diffusion process which occurs in a furnace at about 2200° F under suitable conditions. The resulting metallurgical make-up of the so-produced substrate can range from a completely homogeneous nickel-chromium alloy to one wherein the concentration of chromium continuously decreases as the center of the substrate is approached. In practice, the actual type of alloy obtained will depend on such parameters as starting foil thickness and time and temperature of the alloying process. Usually, a homogeneous alloy is utilized.

The above-described structure constitutes the substrate to which a highly active NO_(x) reducing material is metallurgically bonded. Catalytic materials suitable for this purpose are copper, nickel, iron, cobalt, manganese and alloys thereof. Recent test data has shown that a catalytic layer consisting of 80 weight percent nickel and 20 weight percent copper has been especially effective in reducing NO.sub. to less harmful substances. The before mentioned catalytic materials are metallurgically bonded to the substrate in a manner that little, if any, of the catalytic material migrates into the substrate or intermediate zone. In practice, any catalytic material which actually migrates into the substrate proper does not significantly affect the chemical and physical properties of the substrate and is not considered as part of the substrate proper. Generally, the catalyst layer constitutes from about 0.5 to about 50 weight percent of the resultant catalytic structure. However, in use all that is required is than an effective amount of catalyst be present.

In the herein described embodiment of the invention, nickel and/or copper, if desired, is electroplated upon the substrate and subsequently metallurgically bonded thereto by diffusion which thereby establishes an outer catalytic zone or layer and an intermediate zone essentially defining the substrate. The diffusion treatment causes part of the chromium in the substrate to migrate toward and into the outer zone or catalytic layer. Microprobe tests have determined that varying amounts of up to about 15 weight percent chromium can be present on the surface of the catalytic layer without seriously affecting its operability as a NO_(x) reduction catalyst at temperatures ranging from about 1100° F to about 1700° F. The exact upper limit of the permissible chromium content in the outer zone and particularly in the surface thereof, under all circumstances is not yet known.

The catalytic structure of the instant invention comprises a nickel base substrate which supports or carries the NO_(x) reducing catalyst. The following table shows substrate compositions which fall within the scope of the instant invention.

    ______________________________________                                         Substrate              Range (In Weight Percent                                Components  Element    of Substrate)                                           ______________________________________                                         Filler Material                                                                            Nickel     48 to 85                                                Filler Material                                                                            Cobalt      0 to  1                                                Filler Material                                                                            Iron        0 to  1                                                Oxide Former                                                                               Chromium*   5 to 50                                                Oxide Former                                                                               Aluminum*   0 to 10                                                ______________________________________                                          *when both chromium and aluminum are present the weight percent of             chromium plus aluminum cannot exceed 50                                  

Particularly good test results have been obtained with a catalytic structure fashioned from a substrate consisting essentially of about 80 weight percent nickel and about 20 weight percent chromium with the catalytic material to be metallurgically bonded thereto consisting essentially of about 80 weight percent nickel and about 20 weight percent copper.

In the preferred practice of the system of the invention the internal combustion engine is operated in a manner such that the exhaust gases therefrom contain relatively low amounts of unreacted oxygen. Preferably less than 1 volume percent of unreacted oxygen is present. Usually, this is accomplished by operating the engine with an air/fuel ratio on the rich side of stoichiometric (rich referring to excess fuel) which is primarily achieved by adjusting the carburetion setting. It is also contemplated to utilize fuel injection as well as other conventional means to supply the engine with the necessary amounts of fuel and oxidant therefor. In the preferred practice of the system of the instant invention it is generally desirable to operate the internal combustion engine in a manner such that the air/fuel ratio generally ranges from about 13.8 to 1 to about 14.5 to 1. However, it will be appreciated by those skilled in the art that depending on the specific fuel utilized, the type of catalyst employed and the temperature at which the gases contact the concerned catalyst this ratio may vary slightly. In general, it can be stated that the ratio of carbon monoxide to oxygen found in the exhaust gas should range from about two to one to about six to one. Clearly, a net reducing atmosphere is to be provided.

The following examples of the invention are for illustrative purposes only and are not intended to limit the scope of the invention.

Example I

A sheet of electrodeposited nickel foil having a thickness of about 0.005 inches was expanded by conventional techniques to produce an open mesh expanded structure having a strand width of about .010 inches and about 10 holes per inch. This sheet of expanded nickel foil was then electroplated with chromium until a 20 percent increase in weight was achieved. Subsequently, the chromium was alloyed with the nickel foil by heating the socoated expanded foil structure at sub-atmospheric pressures (one-half atmosphere of argon) at a temperature of about 2200° F for a period of about 2 hours. The composition of the resulting substrate was about 80 weight percent nickel and about 20 weight percent chromium. The complete surface of the so-produced substrate was then electroplated with copper to provide a coating thickness of about 0.0002 inches. The copper was then diffusion bonded to the substrate by heating the copper coated article at sub-atmospheric pressure (one-half atmosphere of argon) to a temperature of about 1900° f for about 2 hours. A one inch diameter disc of the foregoing catalytic structure had a surface area of about 0.78 square inches.

Example II

A catalytic structure was produced as described in Example I except that:

(1) the open mesh, expanded nickel base structure has a strand width of 0.015 inches, and

(2) the resultant structure of Example I was provided electrolytically on all surfaces with a 0.0002 inch thick coating of nickel which was diffused into the catalytic structure by heating it in a reduced atmosphere (one-half atmosphere of argon) at 1900° F for 2 hours. A one inch diameter disc of the catalytic structure of this example had a surface area of about 0.75 square inches.

An examination of the resultant catalytic structure showed that the surface of the catalytic layer contained about 10 weight percent chromium, 49 weight percent nickel and 41 weight percent copper, and that the catalytic layer constituted about 12 weight percent of the catalytic structure, excluding the surface chromium.

Example III

A catalytic structure was produced as described in Example II except that:

(1) the thickness of the electrodeposited nickel foil was .002 inches, and

(2) the catalyst layer consisted of nickel only which was applied to the substrate by electroplating a 0.001 inch thick layer of nickel on all surfaces of the substrate and then metallurgically bonding the catalytic layer and substrate together by heating the composite structure at 1900° F for 2 hours at sub-atmospheric pressure (one-half atmosphere).

A metallurgical examination of the resultant catalytic structure showed that the surface of the catalytic layer consisted of essentially 100 weight percent nickel and that the catalytic layer constituted about 45 weight percent of the catalytic structure.

With regard to catalytic structures of the foregoing type, recent tests have shown that they exhibit remarkably superior performance characteristics with respect to the reduction of NO_(x) when compared to any known NO_(x) reducing catalytic structure. Specifically, catalysts of the type described in Example II have been tested in a conventional 1970 model year 350 cubic inch V-8 engine with the result being that the NO_(x) content of the exhaust gas has been reduced in excess of 90% over the same engine without a NO_(x) catalyst, i.e., the so-treated exhaust gas contained less than 0.4 grams of NO_(x) per mile. At this time, the exact mechanism which makes these results possible is not yet completely understood. It may reside in the chemistry of the system, the use of expanded metal foil, the interaction of the materials, or a combination thereof.

Catalysts of the type described herein have been utilized in a system for operating an internal combustion engine (as described relative to FIG. 4) with a high degree of success. Such a system when used in conjunction with a conventional oxidation catalyst provides an ideal method for reducing NO_(x), carbon monoxide and unburned hydrocarbon content of automotive exhaust gases.

While the discussion herein has, in the main, concerned an open mesh substrate structure obtained by expanding metal, it will be readily appreciated by those skilled in the art that an open mesh structure can also be achieved by such techniques as slip casting, roll forming, perforating metal sheet, direct electroplating of an open mesh structure, joining strands of fibers together and the like.

As can be seen from a review of the foregoing, the instant invention concerns an article for reducing the NO_(x) content of the exhaust gas stream emanating from the internal combustion engine and a method of using such an article which comprises bringing the exhaust gas stream into contact with a NO_(x) reducing structure of the type herein described which includes an oxidation resistant substrate having an effective amount of a NO_(x) reducing catalyst on the surface thereof.

While there have been described what are at present considered to be the preferred embodiments of this invention, it will be obvious to those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as hereinafter claimed. 

What is claimed is:
 1. In the combination comprising an internal combustion engine and a catalyst for catalytically reducing nitrogen oxides in the exhaust gases of said engine, the improvement wherein said catalyst comprises an apertured, thin, expanded metal foil structure comprising a corrosion resistant nickel base substrate having an effective amount of NO_(x) reducing catalyst metallurgically bonded on the surface thereof, said substrate before metallurgical bonding of said NO_(x) catalyst comprising:from about 50 to about 85 weight percent of a metal selected from the group consisting of nickel, a mixture of nickel and iron, a mixture of nickel and cobalt, and a mixture of nickel, iron and cobalt, with nickel always being present in an amount equal to at least about 48 weight percent of the substrate and the weight percent of iron and cobalt individually never exceeding about 1 percent; and from about 15 to about 50 weight percent of a metal selected from the group consisting of chromium, aluminum and mixtures thereof with at least about 5 weight percent of chromium always present in the substrate and the amount of aluminum never exceeding about 10 weight percent, the chemical composition of said substrate being different than the chemical composition of the catalytic layer.
 2. The combination of claim 1 wherein said NO_(x) reducing catalyst comprises a metal selected from the group consisting of nickel, cobalt, iron, manganese, copper and mixtures thereof.
 3. The combination of claim 2 wherein said NO_(x) reducing catalyst is an alloy of copper and nickel.
 4. The combination of claim 3 wherein said NO_(x) reducing catalyst consists essentially of 80 weight percent nickel and 20 weight percent copper.
 5. The combination of claim 1 wherein said expanded thin metal has a thickness of less than about 0.010 inches.
 6. The combination of claim 1 wherein said catalytic layer constitutes from about 0.5 weight percent to about 50 weight percent of said catalytic structure.
 7. The combination of claim 1 wherein the surface of said catalytic layer contains less than about 15 weight percent of chromium.
 8. The combination of claim 7 wherein the weight percent of chromium on the surface of the catalytic layer is less than the weight percent of chromium in the substrate.
 9. The combination of claim 3 wherein said chromium is present as a gradient of concentration, the concentration in said substrate being a maximum and the concentration in said surface being essentially zero.
 10. The combination of claim 1 wherein the surface of said catalytic layer contains less than about 4 weight percent aluminum. 